The properties of poly(alkylthiophenes) in solution are found to have a profound impact on the self assembly process and thus the microstructural and electrical properties of the resultant thin films. Ordered supramolecular precursors can be formed in regioregular poly(3‐hexylthiophene) (P3HT) solutions through the application of low intensity ultrasound. These precursors survive the casting process, resulting in a dramatic increase in the degree of crystallinity of the thin films obtained by spin coating. The crystallinity of the films is tunable, with a continuous evolution of mesoscale structures observed as a function of ultrasonic irradiation time. The photophysical properties of P3HT in solution as well in the solid state suggest that the application of ultrasound leads to a π stacking induced molecular aggregation resulting in field effect mobilities as high as 0.03 cm2 V−1 s−1. A multiphase morphology, comprising short quasi‐ordered and larger, ordered nanofibrils embedded in a disordered amorphous phase is formed as a result of irradiation for at least 1 min. Two distinct regions of charge transport are identified, characterized by an initial sharp increase in the field effect mobility by two orders of magnitude due to an increase in crystallinity up to the percolation limit, followed by a gradual saturation where the mobility becomes independent of the thin film microstructure.

The self‐organization of organic polymer semiconductors into ordered supramolecular assemblies commensurate with efficient charge transport is achieved by tuning a range of process parameters (e.g., film deposition method (spin vs drop cast), solvent boiling point (low vs high boiling point), polymer‐dielectric interface treatment, and post‐deposition processing (solvent vapor or thermal annealing)). However, these strategies present limitations for large‐scale high‐throughput processing due to associated pre‐ and/or post semiconductor deposition steps. Here, photoinduced anisotropic supramolecular assembly of P3HT chains in solution is demonstrated. UV irradiation provides for enhanced intramolecular ordering of solubilized polymer chains, and thereby effects formation of anisotropic supramolecular polymer assemblies via favorable π–π stacking (intermolecular interaction). Molecular ordering is thus dramatically enhanced with concomitant, enhanced charge transport characteristics of corresponding films. Additional pre‐ and/or post treatments are avoided.

Photopolymers broadly comprise monomers, oligomers, polymers, or mixtures of the aforementioned materials that upon exposure to light undergo photochemical reactions that result in deep-seated changes in their structures which substantially modify their chemical and mechanical properties. Photopolymers may possess chromophores that provide for their intrinsic photosensitivity. Alternatively, other photosensitive molecules may be added that directly or indirectly interact with the photopolymer upon exposure to light to produce the desired property changes. Examples of various types of photopolymers will be presented in this article along with examples of their use in representative applications.

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An inverse relationship between mechanical ductility and mobility/molecular ordering in conjugated polymer systems was determined definitively through systematic interrogation of poly(3-hexylthiophene) (P3HT) films with varied degrees of molecular ordering and associated charge transport performance. The dilemma, whereby molecular ordering required for efficient charge transport conclusively undermines the applicability of these materials for stretchable, flexible device applications, was resolved using a polymer blend approach. Specifically, the molecular interactions between dissimilar polymer materials advantageously induced semiconducting polymer ordering into efficient π−π stacked fibrillar networks. Changes in the molecular environment surrounding the conjugated polymer during the elastomer curing process further facilitated development of high mobility networked semiconductor pathways. A processed P3HT: poly(dimethylsiloxane) (PDMS) composite afforded a semiconducting film that exhibits superior ductility and notable mobility versus the single-component polymer semiconductor counterpart.